具有爪形季铵化侧链的聚苯醚的合成

Synthesis of poly(2,6-dimethyl-1,4-phenylene oxide)containing claw-type quaternized side chains

为了探索制备高性能碱性阴离子交换膜的新途径,以商业化的3,4,5三羟基苯甲酸甲酯、3二甲基氨基1丙醇和3溴丙炔为初始原料,通过光延反应、还原反应、威廉姆逊醚合成法和季铵化反应等反应,合成了一种含有3个季铵盐基团的新侧链前体(MBTTA);通过点击化学将MBTTA接枝到叠氮化聚苯醚上,制得一类具有爪形季铵化侧链的聚苯醚(TQPPO-x-I);通过FT-IR、1H NMR对MBTTA、TQPPO-x-I进行结构表征。热重分析表明TQPPO-x-I具有良好的热稳定性;透射电镜分析表明TQPPO-x-OH膜具有明显的微相分离结构;电导率测试表明,TQPPO-20-OH膜在30、80℃时的离子传导率分别为43.0、85.5 mS/cm。

To explore new approaches to prepare high-performance AAEMs,in this paper,a new side-chain precursor with three quaternary ammonium groups(MBTTA)was first synthesized from commercially available methyl 3,4,5 trihydroxybenzoate,3 amino 1 propanol and 3 bromopropyne by Mitsunobu reaction,Williamson ether synthesis and Menschutkin reaction,and then a novel class of AAEMs based on poly(2,6 dimethyl 1,4 phenylene oxide)containing claw-type quaternized side chains(TQPPO-x-I)were prepared by grafting MBTTA onto azided poly(2,6 dimethyl 1,4 phenylene oxide)s via click chemistry.The structures of MBTTA and TQPPO-x-I were characterized by FT-IR and 1H NMR.The thermogravimetric analysis shows that TQPPO-x-I polymers have good thermal stabilities.Transmission electron microscope images shows that TQPPO-x-OH membranes have obvious microphase separation.Ion conductivity test indicates that the TQPPO-20-OH membrane exhibits ion conductivity of 43.0 mS/cm and 85.5 mS/cm at 30℃and 80℃,respectively.